Poly-(imino(2,5-dialkoxycarbonyl-1,4-phenylene)iminoarylene)

ABSTRACT

A NEW HIGH POLYMER COMPRISING RECURRING STRUCTURAL UNITS OF THE FORMULA   -(2-(R1-OOC-),5-(R2-OOC-)-1,4-PHENYLENE)-NH-(1,4-PHENYL-   ENE)-R3-NH-   AND ADDITIONALLY RECURRING STRUCTURAL UNITS OF THE FORMULA   -(9-(O=),6-(R1-OOC-)ACRIDAN-7,2-YLENE)-R3-NH-   IS OBTAINED BY OXIDATION OF HIGH POLYMER COMPRISING RECURRING STRUCTURAL UNITS OF THE FORMULA   -(2-(R1-OOC-),5-(R2-OOC-)CYCLOHEXA-1,4-DIEN-1,4-YLENE)-   NH-(1,4-PHENYLENE)-R3-NH-   WHICH MAY BE OBTAINED FROM A REACTION BETWEEN DIALKYL SUCCINYL-SUCCINATES AND AROMATIC DIAMINES. THE NEW HIGH POLYMER IS A HEAT RESISTANCE BEING CHARACTERIZED BY SPECTROSCOPIC ABSORPTION IR SPECTRA AT THE VICINITIES OF 2.59, 5.92, 6.38, 6.50, 9.10, 9.50, 11.5 AND 12.7U. IT CAN BE USED TO MAKE FILMS, SHEETS, COATINGS FOR METALS AND AS VARIOUS SHAPED MOLDINGS.

United States Patent Oice Patented July 17, 1973 3,746,684 POLY-[IMINO(2,5DIALKOXYCARBONYL1,4- PHENYLENEHMINOARYLENE] Kazuo Adach, Akira Tai, Fukuji Higashi, and Katsuya Shibata, Tokyo, Japan, assignors to Tekkosha Co., Ltd.,

Tokyo, Japan Filed Oct. 18, 1971, Ser. No. 189,877 Claims priority, applicatiox Japan, Oct. 20, 1970,

Inc. ci. eosg17/o2, 33/06 U.S. Cl. 260-47 CP 6 Claims ABSTRACT F THE DISCLOSURE A new high polymer comprising recurring structural units of the formula V GOOR:

and additionally recurring structural units of the formula is obtained by oxidation of high polymer comprising recurring structural units of the formula COORz which may be obtained from a reaction between dialkyl succinyl-succinates and aromatic diamines. The new high polymer is a heat resistant resin being characterized by spectroscopic absorption IR spectra at the vicinities of 2.59, 5.92, 6.38, 6.50, 6.55, 9.10, 9.50, 11.5 and 12.7;t. It can be used to make films, sheets, coatings for metals and as various shaped moldings RIOOC i i BACKGROUND OF THE INVENTION Field of the invention This invention relates to a new high polymer which is obtained by the oxidation of high polymer comprising recurring structural units of the formula I" Hz I cooRi `I RIOOGUNH-Q-m-NH- Hz .j

wherein R1 and R2 represent C1C4 alkyl radicals, R3 represents an aromatic divalent radical of phenylene derivatve, preferably a member selected from the group consisting of -o-cH-CHrO-,

Description of the prior art Heretofore, there has been known the high polymer, hereinafter sometimes referred to as Polymer II, comprising recurring structural units of the formula I- mcoom alooc/ Niet-@Ramn- Hz i (S. Kimura, Macromol., Chem., 117, 203 (1968)).

SUMMARY OF THE INVENTION A main object of this invention is to provide a new high polymer hereinafter sometimes referred to as Polymer I comprising recurring structural units of the formula V GOOR:

....@Rtml wherein R1 and R2 represent C1-C4 alkyl radicals, R3 represents an aromatic divalent radical of phenylene derivative, preferably a member selected from the group consisting of Another object of this invention is to provide a new high polymer comprising recurring structural units of the rformula COOR; Y

and further recurring structural units of the formula wherein R1, R2 and R3 have the same meaning as above.

A further object of this invention is to provide a process for preparing the new high polymer by oxidizing a high polymer obtained by condensation between succinyl succinates and aromatic diamines.

A still further yobject of this invention is to provide a new high polymer which shows good resistance to heat, acids and alkalies, as Well as to dielectric breakdown, and

has excellent properties of strong adhesion, good electricv insulation and the like.

3 BRIEF DESCRIPTION F THB DRAWING The drawing shows an absorption IR spectrum olf a typical polymer of this invention which is obtained by oxidizing with air the polymer derived from the reaction between diethyl succinylsuccinate and 4,4diaminodiphenyl ether (the first polymer is hereinafter refered to as Polymer I1 and the second as Polymer Ill), together with that of Polymer II2. The solid line shows the IR spectrum of Polymer I1 and the dashed line shows that of Polymer H1.

DETAILED EXPLANATION OF THE INVENTION The high polymer, Polymer I, of this invention shows characteristic IR absorptions at the vicinities of 2.59, 5.90, 6.50, 9.10, 11.5 and 12.7n. As is obviously recognized from the spectra in the drawing, the characteristic IR absorptions of Polymer H1 at 6.25 and 6.09p, which are due to the stretching of double bond off cyclohexadiene Skelton and to the stretching of carbonyl being greatly shifted to longer wavelength by the effect of the conjugation with the double bond and further of hydrogen bonding with amine radical, respectively, disappear in the Polymer I1. Instead of these, the IR absorptions at 5.90 and 11.5,u appear and these are due to the stertching of carbonyl in the ester of aromatic carboxylic acids and to the stretching of the aromatic double bond in tetra-substituted benzene skeleton, respectively.

The Polymer I of the present invention also show the absorption of IR spectrum at 2.59, 6.50, 9.10 and 12.7# as mentioned above. Therefore, it is confirmed that the Polymer I of this invention comprises recurring structural units of the formula GOOR,

The conversion reaction of Polymer II to Polymer I can be explained in the case, cfor example, of Polymer II, by the following equations;

--HzoI The Polymer II is converted to Polymer I of this invention by the oxidation of the cyclohexadiene ring in 70 tained the recurring structural units to a benzene ring, and at the same time the ring closure reaction occurs to form an acridone structure by the dealcoholation reaction. These two reactions occur concurrently, but since the than that of the ring closure reaction, the ratio of the recurring structural units including the acridone ring is usually 5-10% to the overall recurring structural units. This'value can be estimated by measuring the quantitatively released Water and alcohol according to the aforementioned reaction processes. It is concluded that the said ring closure reaction hardly occurs subsequent to the oxidation reaction.

The afore-mentioned reaction processes were confirmed by analyzing the results obtained from such techniques as absorption IR spectroscopy, differential thermal analysis and the analysis using a thermal balance, and also by tracing the condensation reaction using diethyl succinyl-succinate and aniline as the model compounds. That is, the Polymer II is converted by heating in the air to the copolymer, Polymer I of this invention, whereby the cyclohexadiene skeleton is oxidized to benzene ring accompanying the partial dealcoholation reaction for forming acridone ring.

The starting material, Polymer l1 of this invention, can be easily obtained by the condensation reaction between dialkyl succinyl-succinates of the formula no @700011, mooolfon (wherein R1 and R2 represent Cl-C, lower alkyl radicals) and diamines of the formula wherein R3 represents an aromatic divalent radical of phenylene derivative, preferably a member selected from the group consisting of by heating in the presence of solvents.

I HtCzOOC COOCQH;

The high polymer, Poly-mer I of this invention, is obby oxidizing the thus obtained starting material high Polymer III. The Polymer II may be applied in the form of a solution onto metal goods such as copper, silver, gold, iron, aluminum or tin, and then oxidized by heating in the air. The oxidation may also be carried reaction velocity of the oxidation reaction is much greater out by heating the starting material high Polymer II in 6 the state of powder, film or molding in air, or in the state film on the plate. The lm was maintained at 120 C. for of a suspension thereof in the presence of an oxidizing l hour under ventilation, and then stripped off from the agent. A temperature of 80-250 C. preferably 15G-200 plate. The film Was fixed between metal amings and C., is employed for the heating. heated further at 200 C. for another 1 hour to obtain No appreciable change is observed in the new heat- 5 a dark red liexible film. resistant resin, Polymer I of this invention, after severe This finally obtained film showed a absorption IR- heating at 180 C. for 1 week and also at 600 C. for a spectrum as illustrated by the solid line in the drawing, moment. which has the characteristic IR-absorptions at 2.59, 5.92,

This resin shows a good durability for alkalis, as illus- 6.50, 9.10, 12.7, 6.38 and 6.55m and is determined to be trated by the fact that no appreciable changes were ob- Polymer I. served even when it was contacted with molten metallic The physical properties of the lm are as follows; sodium or hot potassium hydroxide solution.

y hardness measured by the pencil scratch test was 3H. No PREFERRED EMBODIMENT OF THE INVENTION appreciable break-down of the resin film was observed This invention is further illustrated by the following on Mandrel-bending test using 5 mm. diameter cylinders nonlimitative examples. Hereinafter, the term part repin which the aluminum plate bearing the adhered resin resents weight part and the measurements of the dielectric film was bent around on the cylinder. properties were carried out at 1 kHz. No appreciable stripping of the cross cut section of the EXAMPLE 1 35 cut tape test in which the square cut sections of the resin A polymerization reaction was carried out by heating Clm of l mm.2 Was pulled by an adhering tape stuck on a solution of 2.56- parts of diethyl succinylsuccinate the cross cut resin film. and 2.00 parts of 4,4'diamino diphenyl ether in 60 parts of dimethyl formamide at 120 C. for 7 hours in a nitro- Example 3 gen atmosphere. The resulting viscous liquidy was cooled 40 A polymerization reaction of 5.12 parts of diethyl sucto room temperature, then poured into 120 parts of water cinylsuccinate with 8.20 parts of 2,2-bis- [4- (Ll-aminoto form a dispersion of the product. The yellow polymer phenoxy)phenyl] propane and the isolation of the resultpowder was obtained by ltermg the dispersion, washing ing polymer was carried out in the similar way as in and drying the iltrate. This yellow polymer which shows Example l to give powder of a Polymer II comprising rethe characteristic 1li-absorption spectrum inherent to the 45 curring structural units of the formula OOCgHs H2 (ISH: I Polymer II as illustrated in the drawing is determined to be Polymer Ill comprising recurring structural units of the formula The polymer film obtained in the similar way as in Example 1 from the polymer solution which is prepared by dissolving 20 parts of the above resulting powder in H z GOOG H parts of m-cresol, Was fixed in a metal framing. Then the lilm was heated C. for 2 hours. 13502000 NH 0 NH The resulting dark red and flexible film had IR absorp- H2 I 60 tiene at 2.59, 5.92, 6.50, 9.10, 12.7, 6.38 and 6.55,.. It

This polymer is cast on a .glass Plate by applying a was confirmed that the iilm consists of a Polymer I corn- 30% solution thereof in cyclohexanone to form a resin prising recurring structural units of the formula T CO OCzHr and further recurring structural units of the formula supi-@OW lilm in 10 x 10 sections thereof was observed on cross,

The physical properties of this Polymer I lm were as follows;

Elongation strength Jrg/mm2-- 9.5

Elongation percent-.. 9.5

Volume resistivity Q-cm-- 1015 Dielectric loss 1.2)(10r3 Dielectric constant 1.9

Dielectric break-down voltage kv./mm 92 Example 4 A polymerization reaction of 2.56 parts of diethyl succinyl-succinate with 4.32 parts of di-[4-(4-aminophenoxy)] phenyl sulphone and the isolation of the resulting Polymer II was carried out in the similar way as in Example 1. From the resulting polymer a film of the Polymer I comprising recurring structural units of the formula C OOCzHs and further recurring structural units of the formula was obtained in the similar way as in Example 1.

The physical properties of the finally resulting film were as follows;

A cast lm of a Polymer II comprising recurring structural units of the formula 8 Example 6 A 30% solution of a Polymer II in cyclohexanone, said Polymer I-I comprising recurring structural units of the formula Y COOCiH;

was prepared from 1.28 parts of diethyl succinyl succinate and 0.92 part of benzidine in the similar way as in Example 1. This solution was doctored onto an iron plate to form a resin film in the similar way as in Example 2, which was subsequently heated in the air at 200 C. for 1 hour resulting in a resin film of a Polymer I comprising 35 recurring structural units of the formula on an aluminum plate was prepared from 1.04 parts of dimethyl succinyl-succinate and 1.22 parts of ethyleneglycol bis(4amino phenyl) ether in the similar way as in Example l.

A resin ilm of the Polymer I comprising recurring structural units of the formula and further recurring structural units of the formula was obtained by heating the cast film of the Polymer II in air at 200 C. for 1 hour. Electric properties of the 70 w nally obtained resin film were as follows:

and recurring structural units of the formula 0 L- C @el 55 HsCzOOC- N/I mcooc NH--O-GHrCm-O--Nnl- -CHPCHFOQsHn H1000 C \N H Electric properties of the finally obtained resin film ere as follows:

Volume resistivity ,Q-cm. 1X 1015 Volume resistivity Q-Cm" 1.1 X 10" Dielectric loss 1.3 X10-3 DiieCtriC lOSS 1.4 X 103 Dielectric constant 2.2 Dielectric constant 2.0 Dielectric break-down voltage kv./mm 89 75 Dielectric break-down voltage v kv./mm 90 3,746,684 9 10 Example 7 Cross cut tape test: No appreciable stripping of cross cut A solution of a Polymer II comprising recurring struc- Sections of the lm was Observed tural units of the formula Volume resistivity: 1.2 1015 Q-cm.

H I I C0004 s (H, I

Hz H3 .J

was prepared from 3.12 parts of dibutyl succinyl-succinate Dielectric loss: 1.2 10"3 and 4.10 parts of 2,2-bis [4-(4-aminophenoxy)phenyl] Dielectric constant: 2.0 propane in the similar way as in Example 1. This solution Dielectric break-down voltage: 90 kv./mm.

was doctored onto an iron plate to form a resin lilm in the similar Way as in Example 2, which was Subsequently The Mandrel-bendlng test and the cross cut tape test heated in the air at 200 C, for 0 5 hour resuhing in a Were carried out in the same manner as in Example 2.

resin lm of a Polymer I comprising recurring structural We claim: units of the formula 1. A film-forming polymer which consists essentially of and further recurring structural units of the formula Electric properties of the nally obtained resin film recurring structural units ofthe formula were as follows:

Volume resistivity Q-cm 1.1 X l015 GOOR,

Dielectric loss 13x10*3 35 Dielectric constant 2.1 RiOOG NH-@ R-NH- Dielectric break-down voltage ..kv./mm 4 91 -l Example 8 wherein R1 and R2 are alkyl radicals having from 1 to 4 carbon atoms, and R3 is a divalent radical selected from A polymerlzatron reaction of 5.12 parts of diethyl suc the group consisting of cinyl succinate and 4.96 parts of 4,4diaminodipheny1 sulfone, both dissolved in 120 parts of dimethyl form- CH,

amide, was carried out in nitrogen atmosphere in the O O (lJ o similar way as in Example 1 to form a Polymer II com- Q prising recurring structural units of the formula HrCzOOC The Polymer II solution was prepared in the same manand ner as in Example 1. 'Ihe solution was doctored onto an aluminum plate in the same manner as in Example 2, which subsequently heated in air at 200 C. for 1 hour resulting in a resin lm of a Polymer I comprising recurz A lmdforming polymer which consists essentiau f y o ng stmctural umts of the formula from about 5% to about 10% of recurring structural units of the formula -COOCzHI I o I Hclooc -NH-rso.-Nn I (ll I J I Unt-NH* and further recurring structural units of the formula Rxooc r 8 N -SOa- I HrCiooC \N NHT and the balance is recurring structural units of the formula -CooRz Physical properties of the finally obtained resin lm were as follows: Rlooo -NH--Rs-NHT Mandrel-bending test: No appreciable break-down of the iilm was observed on 5 mm. diameter cylinder 75 wherein R1 and R2 are alkyl radicals having from 1 to 4 carbon atoms, and R3 is a divalent radical selected from the group consisting of and 3. A process for preparing a polymer which comprises oxidizing with an oxidizing agent at a temperature of 80 to 250 C. a first polymer consisting essentially of recurring structural units of the formula until there is formed a substantial amount of a second polymer consisting essentially of recurring structural units of the formula COOR:

'-11100 o NH-@ Rs-Nnl wherein R1 and R2 are alkyl radicals having from 1 to 4 carbon atoms, and R3 is a divalent radical selected from the group consisting of 4. The process according to claim 1, wherein a lm of the rst polymer is oxidized, thereby producing a lm of the second polymer.

5. The process according to claim 1, wherein the rst polymer is a polymer obtained by a polymerization reaction between a succinyl succinate of the formula Hz EIO-1 I COORz R() OH and a diamine of the formula wherein R1 and R2 are radicals selected from the group consisting of methyl, ethyl, propyl and butyl, and R3 is a radical selected from the group consisting of 6. The process according to claim 3, wherein the second polymer further contains from about 5% to about 10% of recurring structural units of the formula /E tzt-Naland the oxidation is carried out at an elevated temperature.

References Cited UNITED STATES PATENTS 3,426,044 2/ 1969 Sparks et al. 260-346.6 3,635,888 1/1972 Adachi et al. 260-47 WILLIAM H. SHORT, Primary Examiner L. L. LEE, Assistant Examiner U.S. Cl. X.R.

117-124 E, 132 B; 260-32.6 N, 32.8 N, 334 P, 49, 65, 78 TF 

